By L. J. Ferry
This exhaustive reference textual content systematically introduces the elemental theories and experimental tools of anionic polymerization in addition to the synthesis, research, and features of anionically polymerized items.
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Extra info for Anionic Polymerization
At concentrations in excess of I 0 -3 molar, a shoulder develops at ca. 260 nm (in addition to the principal absorption maximum at 316 rim) which was attributed to the formation of aggregated species. Garton and Bywater ~92) studied the anionic polymerization of butadiene in T H F using both lithium and sodium as counterions. They found that the spectrum recorded during polymerization depends upon the temperature as shown in Fig. 14. On completion of the polymerization at --40 °C the spectrum changed, the intensity at longer wavelength decreasing while that at short wavelength increased.
They were unable to distinguish between addition of monomeric n-butyllithium and that of the species (n-BuLi: TMEDA) to the monomer as the initiation step. 35 and it was concluded that propagation involves growth from the loose (solvent separated) ion pair of composition (PBLi • 2 TMEDA). The presumption that there is no exchange of TMEDA among the complexed species is not in accordance with the observation of time-averaged signals in the ~H-NMR spectrum 181) Vinogradova et al. 18z) found that the rate of polymerization of butadiene in petroleum ether at 20 °C reaches a maximum value when the ratio of ~MEDA]:[Li] is about 4.
5 to 1 molar), Magnin et al. 3 M) concentrations. As they remarked, with [BuLi] = [TMEDA] = 1 M, some 30 % (v/v) of the reaction mixture is TMEDA-a situation very different from that at lower concentration. Anionic Polymerizationsof Non-Polar Monomers Involving Lithium 37 One feature of the earlier work of Schue et al. 174)that does not fit their subsequently proposed mechanism 173) is their observation that the propagation rate is directly proportional to the initiator concentration when F M E D A ] = [t-BuLi].